Electronic devices including carbon-based films having sidewall liners, and methods of forming such devices

ABSTRACT

Methods in accordance with aspects of this invention form microelectronic structures in accordance with other aspects of this invention, such as non-volatile memories, that include (1) a layerstack having a pattern including sidewalls, the layerstack comprising a resistivity-switchable layer disposed above and in contact with a bottom electrode, and a top electrode disposed above and in contact with the resistivity-switchable layer; and (2) a dielectric sidewall liner in contact with the sidewalls of the layerstack; wherein the resistivity-switchable layer includes a carbon-based material, and the dielectric sidewall liner includes an oxygen-poor dielectric material. Numerous additional aspects are provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Patent Application Ser. No. 61/081,029, filed 15 Jul. 2008, “METHODS FOR ETCHING CARBON NANO-TUBE FILMS” (the '029 application), which is incorporated by reference herein in its entirety for all purposes. (Docket No. MXA-315P).

FIELD OF THE INVENTION

This invention relates to microelectronic devices, such as non-volatile memories, and more particularly to electronic devices including carbon-based films having sidewall liners, and methods of forming the same.

BACKGROUND

Non-volatile memories formed from reversible resistance-switching elements are known. For example, U.S. patent application Ser. No. 11/968,154, filed Dec. 31, 2007, titled “MEMORY CELL THAT EMPLOYS A SELECTIVELY FABRICATED CARBON NANO-TUBE REVERSIBLE RESISTANCE-SWITCHING ELEMENT AND METHODS OF FORMING THE SAME” (hereinafter “the '154 Application”), which is hereby incorporated by reference herein in its entirety for all purposes, describes a rewriteable non-volatile memory cell that includes a diode coupled in series with a carbon-based reversible resistivity-switching material such as carbon.

However, fabricating memory devices from rewriteable resistivity-switching materials is technically challenging, and improved methods of forming memory devices that employ resistivity-switching materials are desirable.

SUMMARY

In some aspects of the invention, a method of forming a microelectronic structure is provided, wherein the method includes (1) forming a layerstack, the layerstack comprising a resistivity-switchable layer and a top electrode above and in contact with the resistivity-switchable layer; (2) etching the layerstack to have a pattern including sidewalls; and (3) forming a dielectric sidewall liner in contact with the sidewalls of the layerstack; wherein the resistivity-switchable layer includes a carbon-based material, and the dielectric sidewall liner includes an oxygen-poor dielectric material.

In other aspects of the invention, a microelectronic structure is provided that includes (1) a layerstack having a pattern including sidewalls, the layerstack comprising a resistivity-switchable layer disposed above and in contact with a bottom electrode, and a top electrode disposed above and in contact with the resistivity-switchable layer; and (2) a dielectric sidewall liner in contact with the sidewalls of the layerstack; wherein the resistivity-switchable layer includes a carbon-based material, and the dielectric sidewall liner includes an oxygen-poor dielectric material.

Other features and aspects of this invention will become more fully apparent from the following detailed description, the appended claims and the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

Features of the present invention can be more clearly understood from the following detailed description considered in conjunction with the following drawings, in which the same reference numerals denote the same elements throughout.

FIG. 1 depicts a cross-sectional, elevational schematic diagram of an exemplary memory cell in accordance with an embodiment of the present invention, the memory cell comprising a sidewall liner surrounding a metal-insulator-metal structure.

FIG. 2 includes FIGS. 2A and 2B, which depict elevational cross-sections of other exemplary memory cells in accordance with embodiments of the present invention, each memory cell comprising a sidewall liner surrounding a metal-insulator-metal structure in series with a diode.

FIG. 3 is a perspective view of an exemplary memory level of a monolithic three dimensional memory array provided in accordance with the present invention.

DETAILED DESCRIPTION

Certain carbon-based films, including but not limited to carbon nanotubes (“CNTs”), graphene, amorphous carbon containing microcrystalline or other regions of graphene, and other graphitic carbon films, etc., may exhibit resistivity switching properties that may be used to form microelectronic non-volatile memories. Such films therefore are candidates for integration within a three-dimensional memory array. For instance, CNT materials have demonstrated memory switching properties on lab-scale devices with a 100× separation between ON and OFF states and mid-to-high range resistance changes. Such a separation between ON and OFF states renders CNT materials viable candidates for memory cells formed using the CNT materials in series with vertical diodes, thin film transistors or other steering elements.

In the aforementioned example, a metal-insulator-metal (“MIM”) stack formed from a carbon-based material sandwiched between two metal or otherwise conducting layers may serve as a resistance change material for a memory cell. Moreover, a carbon-based MIM stack may be integrated in series with a diode or transistor to create a read-writable memory device as described, for example, in the '154 Application.

In accordance with exemplary embodiments of the present invention, methods and apparatus may involve a microelectronic structure, such as a memory device, having a carbon-based resistivity-switchable layer in an MIM stack, and the MIM may include a dielectric sidewall liner that protects the carbon-based layer against deterioration that may occur during deposition of dielectric gap fill material. The MIM may be integrated in series with a steering element, such as a diode, to form a memory cell.

The carbon-based resistivity-switching material may include carbon in many forms, including CNTs, graphene, graphite, amorphous carbon, graphitic carbon and/or diamond-like carbon. The nature of the carbon-based layer may be characterized by its ratio of forms of carbon-carbon bonding. Carbon typically bonds to carbon to form either an sp²-bond (a trigonal double C═C bond) or an sp³-bond (a tetrahedral single C—C bond). In each case, a ratio of sp²-bonds to sp³-bonds can be determined via Raman spectroscopy by evaluating the D and G bands. In some embodiments, the range of materials may include those having a ratio such as M_(y)N_(z) where M is the sp³ material and N is the sp² material and y and z are any fractional value from zero to 1 as long as y+z=1. Diamond-like carbon comprises mainly sp³-bonded carbon and may form an amorphous layer.

Depending on the carbon-based material desired, different formation techniques may be used. For instance, pure carbon nanotubes may be deposited by CVD growth techniques, colloidal spray on techniques, and spin on techniques. Additionally, carbon material deposition methods may include, but are not limited to, sputter deposition from a target, plasma-enhanced chemical vapor deposition (“PECVD”), PVD, CVD, arc discharge techniques, and laser ablation. Deposition temperatures may range from about 300° C. to 900° C. A precursor gas source may include, but is not limited to, hexane, cyclo-hexane, acetylene, single and double short chain hydrocarbons (e.g., methane), various benzene based hydrocarbons, polycyclic aromatics, short chain ester, ethers, alcohols, or a combination thereof. In some cases, a “cracking” surface may be used to promote growth at reduced temperatures (e.g., about 1-100 angstroms of iron (“Fe”), nickel (“Ni”), cobalt (“Co”) or the like, although other thicknesses may be used).

In some embodiments, the carbon-based resistivity-switching material may be composed of amorphous carbon or a dielectric filler material mixed with graphitic carbon, deposited in any of the above mentioned techniques. A particular embodiment of this integration scheme includes a spin or spray application of the CNT material, followed by deposition of amorphous carbon from an Applied Materials, Inc., Producer™ tool for use as carbon-based liner material. The optional carbon-based protective liner can be deposited using a deposition technique similar to or different than that used to deposit the CNT material.

The carbon-based resistivity-switching material may be deposited in any thickness. In some embodiments, the carbon-based resistivity-switching material may be between about 1-1000 angstroms, although other thicknesses may be used. Depending on device construction, such as described herein, preferred ranges may include 200-400 angstroms, 400-600 angstroms, 600-800 angstroms, and 800-1000 angstroms.

Exemplary Embodiments

In accordance with a first exemplary embodiment of this invention, formation of a microelectronic structure includes formation of an MIM device having a carbon film disposed between a bottom electrode and a top electrode, the carbon film comprising, for instance, a resistivity-switchable CNT layer. The structure also includes a dielectric sidewall liner provided to protect the carbon-based material from degradation during a dielectric fill step.

FIG. 1 is a cross-sectional elevational view of a first exemplary microelectronic structure 100, also referred to as memory cell 100, provided in accordance with this invention. Memory cell 100 includes a first conductor 102 formed over a substrate (not shown), such as over an insulating layer over the substrate. First conductor 102 may include a first metal layer 104, such as a tungsten (“W”), copper (“Cu”), aluminum (“Al”), gold (“Au”), or other metal layer. First conductor 102 may comprise a lower portion of an MIM layerstack structure 105 and function as a bottom electrode of MIM 105. An adhesion layer 106, such as a tungsten nitride (“WN”), titanium nitride (“TiN”), tantalum nitride (“TaN”), molybdenum (“Mo”), or similar layer, is optional but is shown in FIG. 1 formed over first metal layer 104. In general, a plurality of the first conductors 102 may be provided and isolated from one another (e.g., by employing silicon dioxide (“SiO₂”) or other dielectric material isolation between each of first conductors 102). For instance, first conductor 102 may be a word-line or a bit-line of grid-patterned array.

A layer of CNT material 108 is formed over first conductor 102 using any suitable CNT formation process. Carbon-based material 108 may comprise a middle portion of MIM layerstack structure 105, and function as an insulating layer of MIM 105. CNT material 108 may be deposited by various techniques. One technique involves spray- or spin-coating a carbon nanotube suspension over first conductor 102, thereby creating a random CNT material. Another technique involves growing carbon nanotubes from a seed anchored to the substrate by CVD, PECVD or the like. Discussions of various CNT deposition techniques are found in the '154 application, and related U.S. patent application Ser. No. 11/968,156, “MEMORY CELL THAT EMPLOYS A SELECTIVELY FABRICATED CARBON NANO-TUBE REVERSIBLE RESISTANCE-SWITCHING ELEMENT FORMED OVER A BOTTOM CONDUCTOR AND METHODS OF FORMING THE SAME,” filed Dec. 31, 2007, and Ser. No. 11/968,159, “MEMORY CELL WITH PLANARIZED CARBON NANOTUBE LAYER AND METHODS OF FORMING THE SAME,” filed Dec. 31, 2007, which are hereby incorporated by reference herein in their entireties for all purposes.

In some embodiments in accordance with this invention, following deposition/formation of CNT material 108, an anneal step may be performed to modify the properties of the CNT material 108. In particular, the anneal may be performed in a vacuum or the presence of one or more forming gases, at a temperature in the range from about 350° C. to about 900° C., for about 30 to about 180 minutes. The anneal preferably is performed in about an 80% (N₂):20% (H₂) mixture of forming gases, at about 625° C. for about one hour.

Suitable forming gases may include one or more of N₂, Ar, and H₂, whereas preferred forming gases may include a mixture having above about 75% N₂ or Ar and below about 25% H₂. Alternatively, a vacuum may be used. Suitable temperatures may range from about 350° C. to about 900° C., whereas preferred temperatures may range from about 585° C. to about 675° C. Suitable durations may range from about 0.5 hour to about 3 hours, whereas preferred durations may range from about 1 hour to about 1.5 hours. Suitable pressures may range from about 1 mT to about 760T, whereas preferred pressures may range from about 300 mT to about 600 mT.

This anneal may be performed prior to the formation of a top electrode above CNT material 108. A queue time of preferably about 2 hours between the anneal and the electrode metal deposition preferably accompanies the use of the anneal. A ramp up duration may range from about 0.2 hours to about 1.2 hours and preferably is between about 0.5 hours and 0.8 hours. Similarly, a ramp down duration also may range from about 0.2 hours to about 1.2 hours and preferably is between about 0.5 hours and 0.8 hours.

Although not wanting to be bound by any particular theory, it is believed that the CNT material may absorb water from the air and/or might have one or more functional groups attached to the CNT material after the CNT material is formed. Organic functional groups are sometimes required for pre-deposition processing. One of the preferred functional groups is a carboxylic group. Likewise, it is believed that the moisture and/or organic functional groups may increase the likelihood of delamination of the CNT material. In addition, it is believed that the functional groups may attach to the CNT material, for instance, during a cleaning and/or filtering process. The post-carbon-formation anneal may remove the moisture and/or carboxylic or other functional groups associated with the CNT material. As a result, in some embodiments, delamination of the CNT material and/or top electrode material from a substrate is less likely to occur if the CNT material is annealed prior to formation of the top electrode over the CNT material.

Incorporation of such a post-CNT-formation anneal preferably takes into account other layers present on the device that includes the CNT material, inasmuch as these other layers will also be subject to the anneal. For example, the anneal may be omitted or its parameters may be adjusted where the aforementioned preferred anneal parameters would damage the other layers. The anneal parameters may be adjusted within ranges that result in the removal of moisture and/or carboxylic or other functional groups without damaging the layers of the annealed device. For instance, the temperature may be adjusted to stay within an overall thermal budget of a device being formed. Likewise, any suitable forming gases, temperatures and/or durations may be used that are appropriate for a particular device. In general, such an anneal may be used with any c-based layer or carbon-containing material, such as layers having CNT material, graphite, graphene, amorphous carbon, etc.

In some embodiments in accordance with this invention, following deposition/formation of CNT material 108, an optional second carbon-based material layer 109 may be formed as a protective liner covering CNT material 108. Carbon-based layer 109 serves as a defensive interface with layers above it, in particular the top electrode layers. Carbon-based layer 109 preferably may include amorphous carbon, but other non-CNT carbon-based materials, such as graphene, graphite, diamond-like carbon, or other variations of sp²-rich or sp³-rich carbon materials. The carbon-based material 109 preferably may be adapted to fill pores in the CNT material 108, and not be overly porous itself. In some embodiments, the additional carbon-based top layer penetrates many of the topside pores of the CNT film, impeding penetration of the top electrode metal into the sealed pores. In some embodiments, the carbon-based liner also reduces and/or prevents damage to the CNT material during top electrode deposition by shielding the CNT material from exposure to the metal deposition process.

Carbon-based material 109 and its thickness also may be selected to exhibit vertical electrical resistance appropriate for memory cell 100 in which it is incorporated, taking into account, for example, preferred read, write, and programming voltages or currents. Vertical resistance, e.g., in the direction of current flow between the two electrodes as shown in FIG. 1, of layers 108 and 109 will determine current or voltage differences during operation of structure 100. Vertical resistance depends, for instance, on material vertical resistivity and thickness, and feature size and critical dimension. In the case of CNT material 108, vertical resistance may differ from horizontal resistance, depending on the orientation of the carbon nanotubes themselves, as they appear to be more conductive along the tubes than between the tubes.

After formation of carbon-based material 109, an adhesion/barrier layer 110, such as TiN, TaN, W, WN, tantalum carbon nitride (“TaCN”), or the like, may be formed over CNT material 108. As shown in FIG. 1, adhesion layer 110 may function as a top electrode of MIM device 105 that includes CNT material 108 and optional carbon-based material 109 as the insulating layer, and first metal layer 104 and optional adhesion layer 106 as the bottom electrode. As such, the following sections refer to adhesion/barrier layer 110 as “top electrode 110” of MIM 105.

In some embodiments in accordance with this invention, top electrode 110 may be deposited using a lower energy deposition technique, e.g., one involving energy levels lower than those used in PVD of similar materials. Such exemplary deposition techniques may include non-conformal deposition, low bias power physical vapor deposition (LBP-PVD), low temperature PVD, and other similar techniques. Use of a non-conformal, lower energy deposition technique to deposit top electrode 110 on the carbon material may reduce the potential for deposition-associated damage to CNT layer 108 and the potential for infiltration and/or penetration of CNT layer 108 by top electrode 110. In embodiments foregoing the use of a carbon liner 109, use of lower energy deposition techniques may be particularly advantageous to limit the deleterious effects of the deposition of top electrode 110. Metal deposition techniques that are non-conformal have a lower likelihood of depositing metal into a pore in the CNT layer 108.

The layerstack of layers 108, 109, and 110 may be patterned, for example, with about 1 to about 1.5 micron, more preferably about 1.2 to about 1.4 micron, of photoresist (“PR”) using standard photolithographic techniques. Thinner PR layers may be used with smaller critical dimensions and technology nodes. In some embodiments, an oxide hard mask may be used below the PR layer to improve pattern transfer and protect underlying layers during etching. Top electrode 110 then may be etched using oxygen (“O₂”), boron trichloride (“BCl₃”) and/or chlorine (“Cl₂”) chemistries, for example. Any suitable etch chemistries may be used. Any suitable etch parameters, flow rates, chamber pressures, power levels, process temperatures, and/or etch rates may be used. In some embodiments, the top electrode 110, carbon-based liner 109, and CNT material 108 may be patterned using a single etch step. In other embodiments, separate etch steps may be used. The etch of top electrode 110 and carbon-based layers 108, 109 proceeds down to first conductor 102 and exposes gap fill material 111. Such an etched layerstack has been observed to have nearly vertical sidewalls 105′ and little or no undercut of the CNT material 108.

After the etch of the top electrode 110 and carbon-based layers 108, 109, the layerstack may be cleaned prior to formation of additional dielectric gap fill 111′. Data indicate that a CNT layer delaminates in EKC type cleans, so after the stack is etched, a dilute hydrofluoric/sulfuric acid clean is performed. Post CNT etch cleaning, whether or not PR ashing is performed before CNT etching, may be performed in any suitable cleaning tool, such as a Raider tool, available from Semitool of Kalispell, Mont. Exemplary post-CNT-etch cleaning may include using ultra-dilute sulfuric acid (e.g., about 1.5-1.8 wt %) for about 60 seconds and ultra-dilute hydrofluoric (“HF”) acid (e.g., about 0.4-0.6 wt %) for 60 seconds. Megasonics may or may not be used. Following such cleaning, no residual photoresist was observed. If photoresist does come into contact with CNT material, the PR is hard to remove, and the electrical performance of the CNT material suffers.

As such, an exemplary sequence of steps to etch and clean the stack is as follows: (1) pattern the PR; (2) transfer the pattern into an oxide hard mask; (3) ash away the PR (an ash tool may be here because the metal protects the CNT); (4) clean using dilute hydrofluoric and sulfuric acid cleans (dilute HF/ sulfuric acid prevents “popcorn” defects that EKC would cause); (5) etch the stack using oxygen in DPS (no post-etch ashing is used because CNT is exposed); and (6) clean again using dilute HF/sulfuric acid cleans. Following the etch and clean steps, a dielectric sidewall liner may be formed.

After cleaning, deposition of gap fill conventionally would occur. Conventional PECVD techniques, however, for depositing dielectric gap fill material 111′ may employ an oxygen plasma component that is created in the initial stages of deposition. This initial oxygen plasma may harm CNT material 108, causing undercutting and poor electrical performance. To avoid such harm, methods in accordance with this invention form a dielectric sidewall liner 118 to protect sidewalls 105′ of CNT material 108 and carbon-based liner 109 during deposition of the remaining gap-fill dielectric 111′ (e.g., SiO₂). Dielectric sidewall liner 118 is deposited using a deposition chemistry that has a low oxygen content, which produces an “oxygen-poor” dielectric. In one exemplary embodiment, a silicon nitride dielectric sidewall liner 118 followed by a standard PECVD SiO₂ dielectric fill 111′ may be used. Whereas stoichiometric silicon nitride is Si₃N₄, silicon nitride (or simply “SiN”) is used herein to refer to stoichiometric and non-stoichiometric silicon nitride alike.

In the embodiment of FIG. 1, dielectric sidewall liner 118 is deposited conformally over the etched layerstack of top electrode/aC/CNT features before gap fill portion 111′, e.g., the remainder of the dielectric gap fill, is deposited. Dielectric sidewall liner 118 preferably covers outer sidewalls 105′ of CNT material 108 and carbon-based liner 109 and isolates them from dielectric fill 111′. If CNT material 108 is overetched, such that etching of underlying dielectric gap fill material 111 occurs, dielectric sidewall liner 118 may extend below CNT material 108.

In some embodiments, dielectric sidewall liner 118 may comprise about 200 to about 500 angstroms of SiN. However, the structure optionally may comprise other layer thicknesses and/or other materials, such as Si_(x)C_(y)N_(z) and Si_(x)O_(y)N_(z) (with low O content), etc., where x, y and z are non-zero numbers resulting in stable compounds.

The defined top electrode/aC/CNT features may be isolated with SiO₂ or other dielectric fill 111′, and then planarized to co-expose top electrode 110, gap fill 111′ and dielectric sidewall liner 118. A second conductor 112 may be formed over the planar surface, exposing top electrode 110. Second conductor 112 may include a barrier/adhesion layer 114, such as TiN, TaN, WN, Mo, or a similar material, and a metal layer 116 (e.g., tungsten or other conductive material).

MIM device 105 may serve as a resistance-switchable memory element for memory cell 100. Carbon layers 108 and 109 may form a resistivity-switchable portion of the memory element of the memory cell, wherein the memory element is adapted to switch between two or more resistivity states. For example, MIM device 105 may be coupled in series with a steering element such as a diode, a tunnel junction, or a thin film transistor (“TFT”). In at least one embodiment, the steering element may include a polycrystalline vertical diode.

Memory operation is based on a bi-stable resistance change in the CNT stackable layer 108 with the application of high bias voltage (e.g., >4 V). Current through the memory cell is modulated by the resistance of CNT material 108. The memory cell is read at a lower voltage that will not change the resistance of CNT material 108. In some embodiments, the difference in resistivities between the two states may be over 100×. The memory cell may be changed from a “0” to a “1,” for example, with the application of high forward bias on the steering element (e.g., a diode). The memory cell may be changed back from a “1” to a “0” with the application of a high forward bias. As stated, this integration scheme can be extended to include CNT materials in series with a TFT or tunnel junction as the steering element instead of a vertical pillar diode. The TFT or tunnel junction steering element may be either planar or vertical.

In accordance with a second exemplary embodiment of this invention, formation of a microelectronic structure includes formation of a diode in series with an MIM device, having a carbon film disposed between a bottom electrode and a top electrode, and a dielectric sidewall liner provided to protect the carbon-based material from degradation during a dielectric fill step. The dielectric liner and its use are compatible with standard semiconductor tooling.

FIG. 2 is a cross-sectional elevational view of an exemplary memory cell structure 200 provided in accordance with the present invention. FIG. 2 comprises FIGS. 2A and 2B, which depict layers of the memory cell formed in different orders. In FIG. 2A, memory cell structure 200 includes a diode disposed below an MIM device having a dielectric sidewall liner and a CNT film disposed between a bottom electrode and a top electrode. In FIG. 2B, memory cell structure 200′ has the diode disposed above the MIM device.

As shown in FIG. 2A, memory cell structure 200 includes a first conductor 202 formed over a substrate (not shown). First conductor 202 may include a first metal layer 203, such as a W, Cu, Al, Au, or other metal layer, with a first barrier/adhesion layer 204, such as a TiN, TaN or similar layer, formed over first metal layer 203. First conductor 202 may comprise a lower portion of an MIM layerstack structure 205 and function as a bottom electrode of MIM 205, as shown in FIG. 2B. In general, a plurality of first conductors 202 may be provided, e.g., patterned and etched, and isolated from one another, e.g., by employing SiO₂ or other dielectric material isolation between each of first conductors 202.

A vertical P-I-N (or N-I-P) diode 206 is formed above first conductor 202. For example, diode 206 may include a polycrystalline (e.g., polysilicon, polygermanium, silicon-germanium alloy, etc.) diode. Diode 206 may include a layer 206 n of semiconductor material heavily doped a dopant of a first-type (e.g., n-type), a layer 206 i of intrinsic or lightly doped semiconductor material, and a layer 206 p of semiconductor material heavily doped a dopant of a second-type (e.g., p-type). Alternatively, the vertical order of diode 206 layers 206 n, 206 i, and 206 p may be reversed, analogous to diode 206 shown in FIG. 2B.

In some embodiments, an optional silicide region 206 s may be formed over diode 206. As described in U.S. Pat. No. 7,176,064, which is hereby incorporated by reference herein in its entirety for all purposes, silicide-forming materials, such as titanium and cobalt, react with deposited silicon during annealing to form a silicide layer. The lattice spacings of titanium silicide and cobalt silicide are close to that of silicon, and it appears that such silicide layers may serve as “crystallization templates” or “seeds” for adjacent deposited silicon as the deposited silicon crystallizes (e.g., the silicide layer enhances the crystalline structure of diode 206 during annealing). Lower resistivity silicon thereby is provided. Similar results may be achieved for silicon-germanium alloy and/or germanium diodes. In some embodiments using silicide region 206 s to crystallize diode 206, silicide region 206 s may be removed after such crystallization, so that silicon region 206 s does not remain in the finished structure.

A TiN or other adhesion/barrier layer or layer stack 207 may be formed above diode 206. In some embodiments, adhesion/barrier layer 207 may comprise a layer stack 207 including a first adhesion/barrier layer 207 a, a metal layer 207 b, such as of W, and a further adhesion/barrier layer 207 c, such as of TiN.

In the event that a layerstack 207 is used, layers 207 a and 207 b may serve as a metal hard mask that may act as a chemical mechanical planarization (“CMP”) stop layer and/or etch-stop layer. Such techniques are disclosed, for example, in U.S. patent application Ser. No. 11/444,936, “CONDUCTIVE HARD MASK TO PROTECT PATTERNED FEATURES DURING TRENCH ETCH,” filed May 31, 2006, which is hereby incorporated by reference herein in its entirety for all purposes. For instance, diode 206 and layers 207 a and 207 b may be patterned and etched to form pillars, and dielectric fill material 211 may be formed between the pillars. The stack may then be planarized, such as by CMP or etch-back, to co-expose gap fill 211 and layer 207 b. Layer 207 c may then be formed on layer 207 b. Alternatively, layer 207 c may be patterned and etched along with diode 206 and layers 207 a and 207 b. In some embodiments, layer 207 c may be eliminated, and the CNT material may interface directly with metal layer 207 b (e.g., W).

Thereafter, a CNT material 208 may be formed over the adhesion/barrier layer or layer stack 207 using any suitable CNT formation process (as described previously). Following deposition/formation of CNT material 208, an optional second carbon-based material layer 209 may be formed as a protective liner covering CNT material 208. Carbon-based liner 209 may be formed as described above. Following deposition/formation of the carbon-based liner 209, a second adhesion/barrier layer 210, such as TiN, TaN, WN, Mo, or the like, is formed over carbon-based liner material 209.

As shown in FIG. 2A, adhesion layer 207 may function as a bottom electrode of MIM layerstack 205 that includes CNT material 208 and optional carbon-based material 209 as the insulating layer, and an adhesion layer 210 as a top electrode. As such, the following sections refer to adhesion/barrier layer 207 as “bottom electrode 207” with respect to FIG. 2A. Similarly, adhesion/barrier layer 210 is referred to as “top electrode 210” of the MIM 205 of FIG. 2A as well as FIG. 2B. Top electrode 210 may be deposited using a lower energy deposition technique, as discussed above. An additional hard mask and/or CMP stop layer 214 also may be formed (as shown).

Before formation of a top conductor 212, which may include an adhesion layer (not shown) and a conductive layer 216, the layerstack may be patterned and etched, as discussed above in reference to FIG. 1. If an etching process was performed to create the pillars mentioned above, then the etch may apply to layers 208, 209, 210, and possibly 207 c and 214. For example, layers 214, 210 may serve as a hard mask and/or CMP stop for CNT material 208 and carbon-based liner 209.

In some embodiments, CNT material 208 and carbon-based liner 209 may be etched using a different etch step than the etch step used for second adhesion/barrier layer 210. In other embodiments, a single etch step may be used. Such an etched film stack has been observed to have nearly vertical sidewalls 205′ and little or no undercut of CNT material 208. In some embodiments, CNT material 208 may be overetched such that etching of underlying dielectric gap fill material 211 may occur.

After the etch of the top electrode 210 and carbon-based layers 208, 209, the layerstack may be cleaned prior to deposition of additional dielectric gap fill 211′. After cleaning, and before deposition of gap fill 211′, a dielectric sidewall liner 218 may be formed with an oxygen-poor deposition chemistry (e.g., without a high oxygen plasma component) to protect the sidewalls 205′ of the CNT material 208 and carbon-based liner 209 during deposition of an oxygen-rich gap-fill dielectric 211′ (e.g., SiO₂). The dielectric sidewall liner 218 also may be referred to as a pre-dielectric fill liner.

In the embodiment of FIG. 2, a silicon nitride dielectric sidewall liner 218 followed by a standard PECVD SiO₂ dielectric fill 211′ may be used. The silicon nitride dielectric sidewall liner 218 may comprise stoichiometric and/or non-stoichiometric silicon nitride. In some embodiments, the dielectric sidewall liner 218 may comprise about 200 to about 500 angstroms of SiN. However, the structure optionally may comprise other layer thicknesses and/or other materials, such as Si_(x)C_(y)N_(z) and Si_(x)O_(y)N_(z) (with low O content), etc., where x, y and z are non-zero numbers resulting in stable compounds.

The dielectric sidewall liner 218 is deposited conformally over the layerstack of top electrode/aC/CNT features before gap fill portion 211′, e.g., the remainder of the dielectric gap fill, is deposited. The dielectric sidewall liner 218 preferably covers the outer sidewalls 205′ of the CNT material 208 and carbon-based liner 209 and isolates them from the dielectric fill 211′. In embodiments in which the CNT material 208 is overetched such that etching of underlying dielectric gap fill material 211 occurs, the dielectric sidewall liner 218 may extend below the CNT material 108.

After the defined layerstack of top electrode/aC/CNT features are isolated, with SiO₂ or other dielectric fill 211′, they are planarized to co-expose top electrode 210, gap fill 211′, and SiN dielectric sidewall liner 218. A second conductor 212 is formed over second adhesion/barrier layer 210, or layer 214, if layer 214 is used as a hard mask and etched along with layers 208, 209, and 210. Second conductor 212 may include a barrier/adhesion layer, such as TiN, TaN, WN, or a similar layer, as shown in FIGS. 1 and 2, and a metal layer 216, such as a W or other conductive layer.

In contrast to FIG. 1, FIG. 2 depicts a layer 214 of tungsten deposited on adhesion/barrier layer 210 before the stack is etched, so that layer 214 is etched as well. Layer 214 may act as a metal hard mask to assist in etching the layers beneath it. Insofar as layers 214 and 216 both may be tungsten, they should adhere to each other well. Optionally, a SiO₂ hard mask may be used.

In one exemplary embodiment, a SiN dielectric sidewall liner 218 may be formed using the process parameters listed in Table 1. Liner film thickness scales linearly with time. Other powers, temperatures, pressures, thicknesses and/or flow rates may be used. For instance, atomic layer deposition (“ALD”) may be useful for deposition of SiN at smaller technology nodes, such as 22 nm. Table 2 includes exemplary parameters for deposition of SiN by ALD.

TABLE 1 PECVD SiN LINER PROCESS PARAMETERS EXEMPLARY PROCESS PARAMETER RANGE PREFERRED RANGE SiH₄ Flow Rate (sccm) 0.1-2.0 0.4-0.7 NH₃ Flow Rate (sccm)  2-10 3-5 N₂ Flow Rate (sccm) 0.3-4   1.2-1.8 Temperature (° C.) 300-500 350-450 Low Frequency Bias (kW) 0-1 0.4-0.6 High Frequency Bias (kW) 0-1 0.4-0.6 Thickness (Angstroms) 200-500 280-330

In particular, Table 2 lists exemplary precursors and the associated exemplary process conditions. ALD SiN may be deposited in cycles in which ALD of Si is followed by ALD of N. In a first cycle, the Si deposition cycle, a silicon precursor is allowed to absorb onto the surface. An anneal optionally may be performed, followed by a second cycle, the N deposition cycle, in which a nitrogen precursor is allowed to absorb and/or react with the adsorbed Si. Each cycle may have a different chamber condition, given that the valves for one cycle totally shut down for the next cycle to avoid deposition occurring in the servicing lines. The number of pairs of cycles determines the overall film thickness.

TABLE 2 ALD SiN LINER PROCESS PARAMETERS PROCESS PARAMETER EXEMPLARY RANGE PREFERRED RANGE Cycle 1 Temp 300° C.-600° C. 350° C.-400° C. Cycle 1 Precusors SiH₂Cl₂, Si₂Cl₆ SiCl₄ Cycle 1 Pressure 10-1000 Torr 100-300 Torr Cycle 1 Dose 2E7-2E12 Liter 9E8-5E10 Liter Cycle 2 Temp 400° C.-700° C. 525° C.-600° C. Cycle 2 Precusors N₂H₄ NH₃ Cycle 2 Pressure 10-1000 Torr 400-600 Torr Cycle 2 Dose 2E7-2E12 Liter 4E10-1E11 Liter Deposition Rate 0.4-1.4 Å/cycle 0.6-0.8 Å/cycle

Preferably after dielectric sidewall liner 218 is deposited, the remaining thicker dielectric fill 211′ may be immediately deposited (e.g., in the same tool). Exemplary SiO₂ dielectric fill conditions are listed in Table 3. Other powers, temperatures, pressures, thicknesses and/or flow rates may be used.

TABLE 3 EXEMPLARY Si0₂ DIELECTRIC FILL PROCESS PARAMETERS EXEMPLARY PROCESS PARAMETER RANGE PREFERRED RANGE SiH₄ Flow Rate (sccm) 0.1-2.0 0.2-0.4 N₂O Flow Rate (sccm)  5-15  9-10 N₂ Flow Rate (sccm) 0-5 1-2 Temperature (° C.) 300-500 350-450 Low Frequency Bias (kW) 0 0 High Frequency Bias (kW) 0.5-1.8   1-1.2 Thickness (Angstroms)  50-5000 2000-3000

Gap fill film thickness scales linearly with time. SiO₂ dielectric fill 211′ can be any thickness, and standard SiO₂ PECVD methods may be used.

Using a thinner SiN dielectric sidewall liner 218 gives a continuous film and adequate protection to the oxygen plasma from a PECVD SiO₂ deposition without the stress associated with thicker SiN films. Additionally, standard oxide chemistry and slurry advantageously may be used to chemically mechanically polish away a thin SiN dielectric sidewall liner 218 before forming conductor 212, without having to change to a SiN specific CMP slurry and pad part way through the polish.

In some embodiments, use of a dielectric sidewall liner may provide high-yielding devices with forward currents in the range from about 10⁻⁵ to about 10⁻⁴ amperes. Additionally, use of a SiN dielectric sidewall liner 218 may provide individual devices with the largest cycles of operation. Moreover, data indicate that using thin SiN as a protective barrier against CNT material degradation during an oxygen-rich dielectric fill improves electrical performance.

As shown in FIG. 2B, microelectronic structure 200′ may include the diode 206 positioned above the CNT material 208, causing some rearrangement of the other layers. In particular, CNT material 208 may be deposited either on an adhesion/barrier layer 204, as shown in FIG. 2A, or directly on lower conductor 202, as shown in FIG. 2B. Tungsten from a lower conductor may assist catalytically in formation of CNT material 208, e.g., if grown. Tungsten also appears to adhere well to carbon. Whereas FIG. 2A depicts a carbon-based liner 209 formed on CNT material 208, FIG. 2B depicts the structure 200′ as omitting optional carbon-based liner 209. An adhesion/barrier layer 210 may be formed directly on carbon-based switching layer 208, followed by formation of diode 206, including possible silicide region 206 s. An adhesion/barrier layer 207 may be formed on diode 206 (with or without silicide region 206 s).

FIG. 2B depicts a layer 214, such as tungsten, on layer 207, and layer 214 may serve as a metal hard mask and/or adhesion layer to metal layer 216 of second conductor 212, preferably also made of tungsten. The stack may be patterned and etched into a pillar, as described above. In some embodiments, the entire layerstack of layers 206, 207, 208, 210, and 214 may be patterned using a single photolithography step.

Above an optional oxide hard mask, or in place thereof, mentioned with respect to FIG. 1, a layer of silicon may be formed and used as a shrinkable hard mask to further reduce the feature size, e.g., critical dimension. In some embodiments, the silicon is amorphous as deposited using a PECVD technique. After patterning the PR layer and etching the pattern into the amorphous silicon to form a silicon hard mask, the silicon hard mask may be shrunk to reduce the critical dimension of the pattern.

Dielectric sidewall liner 218 may be deposited conformally on the pillar and dielectric fill 211 that isolates first conductors 202. In this case, dielectric sidewall liner 218 may extend upward along the entire height of the layerstack between first conductor 202 and second conductor 212. Planarization to co-expose the gap fill 211′, metal hard mask layer 214, and dielectric sidewall liner 218 is followed by formation of top conductor 212 to achieve the structure 200′ shown in FIG. 2B.

In accordance with a third exemplary embodiment of this invention, formation of a microelectronic structure includes formation of a monolithic three dimensional memory array including memory cells, each memory cell comprising an MIM device having a carbon-based memory element disposed between a bottom electrode and a top electrode and covered by a dielectric sidewall liner. The carbon-based memory element may comprise an optional carbon-based protective layer covering undamaged, or reduced-damage, CNT material that is not penetrated, and preferably not infiltrated, by the top electrode. The top electrode in the MIM optionally may be deposited using a lower energy deposition technique.

FIG. 3 shows a portion of a memory array 300 of exemplary memory cells formed according to the third exemplary embodiment of the present invention. A first memory level is formed above the substrate, and additional memory levels may be formed above it. Details regarding memory array formation are described in the applications incorporated by reference herein, and such arrays may benefit from use of the methods and structures according to embodiments of the present invention.

As shown in FIG. 3, memory array 300 may include first conductors 310 and 310′ that may serve as wordlines or bitlines, respectively; pillars 320 and 320′ (each pillar 320, 320′ comprising a memory cell); and second conductors 330, that may serve as bitlines or wordlines, respectively. First conductors 310, 310′ are depicted as substantially perpendicular to second conductors 330. Memory array 300 may include one or more memory levels. A first memory level 340 may include the combination of first conductors 310, pillars 320 and second conductors 330, whereas a second memory level 350 may include second conductors 330, pillars 320′ and first conductors 310′. Fabrication of such a memory level is described in detail in the applications incorporated by reference herein.

Embodiments of the present invention are useful in formation of a monolithic three dimensional memory array. A monolithic three dimensional memory array is one in which multiple memory levels are formed above a single substrate, such as a wafer, with no intervening substrates. The layers forming one memory level are deposited or grown directly over the layers of an existing level or levels. In contrast, stacked memories have been constructed by forming memory levels on separate substrates and adhering the memory levels atop each other, as in Leedy, U.S. Pat. No. 5,915,167. The substrates may be thinned or removed from the memory levels before bonding, but as the memory levels are initially formed over separate substrates, such memories are not true monolithic three dimensional memory arrays.

A related memory is described in Herner et al., U.S. patent application Ser. No. 10/955,549, “NONVOLATILE MEMORY CELL WITHOUT A DIELECTRIC ANTIFUSE HAVING HIGH- AND LOW-IMPEDANCE STATES,” filed Sep. 29, 2004 (hereinafter the '549 application), which is hereby incorporated by reference herein in its entirety for all purposes. The '549 application describes a monolithic three dimensional memory array including vertically oriented p-i-n diodes like diode 206 of FIG. 2. As formed, the polysilicon of the p-i-n diode of the '549 application is in a high-resistance state. Application of a programming voltage permanently changes the nature of the polysilicon, rendering it low-resistance. It is believed the change is caused by an increase in the degree of order in the polysilicon, as described more fully in Herner et al., U.S. patent application Ser. No. 11/148,530, “NONVOLATILE MEMORY CELL OPERATING BY INCREASING ORDER IN POLYCRYSTALLINE SEMICONDUCTOR MATERIAL,” filed Jun. 8, 2005 (the “'530 application”), which is incorporated by reference herein in its entirety for all purposes.

Another related memory is described in Herner et al., U.S. Pat. No. 7,285,464, (the “'464 patent”), which is incorporated by reference herein in its entirety. As described in the '464 patent, it may be advantageous to reduce the height of the p-i-n diode. A shorter diode requires a lower programming voltage and decreases the aspect ratio of the gaps between adjacent diodes. Very high-aspect ratio gaps are difficult to fill without voids. A thickness of at least 600 angstroms is preferred for the intrinsic region to reduce current leakage in reverse bias of the diode. Forming a diode having a silicon-poor intrinsic layer above a heavily n-doped layer, the two separated by a thin intrinsic capping layer of silicon-germanium, will allow for sharper transitions in the dopant profile, and thus reduce overall diode height.

In particular, detailed information regarding fabrication of a similar memory level is provided in the '549 application and the '464 patent, previously incorporated. More information on fabrication of related memories is provided in Herner et al., U.S. Pat. No. 6,952,030, “A HIGH-DENSITY THREE-DIMENSIONAL MEMORY CELL,” owned by the assignee of the present invention and hereby incorporated by reference herein in its entirety for all purposes. To avoid obscuring the present invention, this detail will be not be reiterated in this description, but no teaching of these or other incorporated patents or applications is intended to be excluded. It will be understood that the above examples are non-limiting, and that the details provided herein can be modified, omitted, or augmented while the results fall within the scope of the invention.

The foregoing description discloses exemplary embodiments of the invention. Modifications of the above disclosed apparatus and methods that fall within the scope of the invention will be readily apparent to those of ordinary skill in the art. Accordingly, although the present invention has been disclosed in connection with exemplary embodiments, it should be understood that other embodiments may fall within the spirit and scope of the invention, as defined by the following claims. 

1. A method of forming a microelectronic structure, the method comprising: forming a layerstack, the layerstack comprising: a resistivity-switchable layer and a top electrode above and in contact with the resistivity-switchable layer; etching the layerstack to have a pattern including sidewalls; and forming a dielectric sidewall liner in contact with the sidewalls of the layerstack; wherein the resistivity-switchable layer includes a carbon-based material, and the dielectric sidewall liner includes an oxygen-poor dielectric material.
 2. The method of claim 1, further comprising: forming a dielectric fill layer around the dielectric sidewall liner; and planarizing to co-expose the dielectric fill layer, the dielectric sidewall liner, and the top electrode.
 3. The method of claim 2, wherein: the pattern comprises a pillar, and forming the dielectric sidewall liner comprises forming a pre-dielectric fill liner around the pillar.
 4. The method of claim 2, wherein: the dielectric fill layer comprises an oxide, and the dielectric sidewall liner comprises a nitride.
 5. The method of claim 1, further comprising: forming a steering element in electrical series with the layerstack; wherein the layerstack further comprises a bottom electrode below and in contact with the resistivity-switchable layer.
 6. The method of claim 5, wherein: the steering element comprises a diode.
 7. The method of claim 5, wherein: the layerstack comprises part of a memory cell.
 8. The method of claim 1, wherein: the carbon-based material comprises carbon nanotubes.
 9. The method of claim 1, wherein: the oxygen-poor dielectric material comprises silicon and nitrogen.
 10. The method of claim 1, wherein: the resistivity-switchable layer of carbon-based material comprises a carbon-based liner above and in contact with a carbon-based active layer.
 11. A microelectronic structure comprising: a layerstack, the layerstack having a pattern including sidewalls, and the layerstack comprising: a resistivity-switchable layer disposed above and in contact with a bottom electrode, and a top electrode above and in contact with the resistivity-switchable layer; and a dielectric sidewall liner in contact with the sidewalls of the layerstack; wherein the resistivity-switchable layer includes a carbon-based material, and the dielectric sidewall liner includes an oxygen-poor dielectric material.
 12. The microelectronic structure of claim 11, further comprising: a dielectric fill layer around the dielectric sidewall liner.
 13. The microelectronic structure of claim 12, wherein: the pattern comprises a pillar, and the dielectric sidewall liner comprises a pre-dielectric-fill liner around the pillar.
 14. The microelectronic structure of claim 12, wherein: the dielectric fill layer comprises an oxide, and the dielectric sidewall liner comprises a nitride.
 15. The microelectronic structure of claim 11, further comprising: a steering element in electrical series with the layerstack; wherein the layerstack further comprises a bottom electrode below and in contact with the resistivity-switchable layer.
 16. The microelectronic structure of claim 15, wherein: the steering element comprises a diode.
 17. The microelectronic structure of claim 15, wherein: the layerstack comprises part of a memory cell.
 18. The microelectronic structure of claim 11, wherein: the carbon-based material comprises carbon nanotubes.
 19. The microelectronic structure of claim 11, wherein: the oxygen-poor dielectric material comprises silicon and nitrogen.
 20. The microelectronic structure of claim 11, wherein: the resistivity-switchable layer of carbon-based material comprises a carbon-based liner above and in contact with a carbon-based active layer.
 21. A method of forming a microelectronic structure, the method comprising: forming a layerstack; etching the layerstack to have a pattern including sidewalls; and forming a dielectric sidewall liner in contact with the sidewalls of the layerstack; wherein the dielectric sidewall liner includes an oxygen-poor dielectric material.
 22. The method of claim 21, further comprising: forming a dielectric fill layer around the dielectric sidewall liner; and planarizing to co-expose the dielectric fill layer, the dielectric sidewall liner, and the layerstack.
 23. The method of claim 22, wherein: the pattern comprises a pillar, and forming the dielectric sidewall liner comprises forming a pre-dielectric fill liner around the pillar.
 24. The method of claim 22, wherein: the dielectric fill layer comprises an oxide, and the dielectric sidewall liner comprises a nitride.
 25. The method of claim 21, wherein: the oxygen-poor dielectric material comprises silicon and nitrogen.
 26. The method of claim 21, wherein: forming the dielectric sidewall liner comprises depositing the dielectric sidewall by plasma enhanced chemical vapor deposition (PECVD).
 27. The method of claim 21, wherein: forming the dielectric sidewall liner comprises depositing the dielectric sidewall by atomic layer deposition (ALD).
 28. The method of claim 27, wherein: the dielectric sidewall liner comprises silicon nitride; and depositing the silicon nitride comprises performing an ALD silicon cycle and an ALD nitrogen cycle.
 29. The method of claim 28, wherein: depositing the silicon nitride further comprises performing an anneal between performing the ALD silicon cycle and performing the ALD nitrogen cycle.
 30. The method of claim 28, wherein: the ALD silicon cycle is performed using first chamber conditions, the ALD nitrogen cycle is performed using second chamber conditions, and the first chamber conditions differ from the second chamber conditions. 